Composite for oil-water separation, synthesis methods and applications of same

ABSTRACT

Certain aspects of the invention relate to a method of synthesizing a composite usably for oil-water separation comprising surface nanostructuring a pristine powder or porous material to form a nanostructured powder or porous material having surfaces with nanoscale features; and coating single or multilayers of one or more low surface energy oligomers, polymers, or their composites with other materials on the surfaces of the nanostructured powder or porous material.

CROSS-REFERENCE TO RELATED PATENT APPLICATION

This application is a divisional application of, and claims benefit ofU.S. patent application Ser. No. 15/904,994, filed Feb. 26, 2018, nowallowed, which itself claims priority to and the benefit of U.S.provisional patent application Ser. No. 62/463,207, filed Feb. 24, 2017,which are incorporated herein by reference in their entireties.

Some references, which may include patents, patent applications andvarious publications, are cited and discussed in the description of thisinvention. The citation and/or discussion of such references is providedmerely to clarify the description of the present invention and is not anadmission that any such reference is “prior art” to the inventiondescribed herein. All references cited and discussed in thisspecification are incorporated herein by reference in their entiretiesand to the same extent as if each reference is individually incorporatedby reference. In terms of notation, hereinafter, [n] represents the nthreference cited in the reference list. For example, [1] represents thefirst reference cited in the reference list, namely, Song, B., Simpleand fast fabrication of superhydrophobic metal wire mesh for efficientlygravity-driven oil/water separation. Marine Pollution Bulletin, 2016.113(1-2): p. 211-215.

FIELD

The present disclosure relates generally to oil-water separation, andmore particularly to a composite for oil-water separation, synthesismethods and applications of the same.

BACKGROUND

The background description provided herein is for the purpose ofgenerally presenting the context of the present disclosure. The subjectmatter discussed in the background of the invention section should notbe assumed to be prior art merely as a result of its mention in thebackground of the invention section. Similarly, a problem mentioned inthe background of the invention section or associated with the subjectmatter of the background of the invention section should not be assumedto have been previously recognized in the prior art. The subject matterin the background of the invention section merely represents differentapproaches, which in and of themselves may also be inventions. Work ofthe presently named inventors, to the extent it is described in thebackground of the invention section, as well as aspects of thedescription that may not otherwise qualify as prior art at the time offiling, are neither expressly nor impliedly admitted as prior artagainst the present disclosure.

When oil spills into water during its offshore production, marinetransport and petrochemicals production, toxic chemicals can be releasedto water and cause pollution, which has become a global problem as itcauses substantial environmental concerns. Oils can also contaminateland water or cause cleaning challenges when spilled over fabricmaterials. Traditional oil-removal methods, which are based on specificgravity of liquids, such as skimming, air floatation, and membranefiltration have been widely used to remove oils from water. Because ofthe high cost of operation and low-efficiency of traditional separationmethods, materials with special wettability, materials that can repelwater (hydrophobic or super-hydrophobic) and absorb oils (oleophilic orsuper-oleophilic), or materials that can repel oils (oleophobic orsuper-oleophobic) and absorb water (hydrophilic or super-hydrophilic),have been used to clean polluted water (oily water) with high separationefficiency. Surface modification, the combination of physics andchemistry working together to modify materials to enhance surfaceproperties, is a key feature in fabricating materials with specialwettability.

Several 3D porous materials have been used to produce materials withspecial wettability [1-4] for oil-water separation purposes including,mesh, foams, sponges, powders, membranes [5-9]. In general, numerousnano-structuring methods have been used to integrate powder or porousmaterials surface with nanostructures to get the essential surfacemorphology (nanostructured) for materials to own special wettabilityafter surface energy reduction. Some well-known examples of fabricationtechniques include chemical vapor deposition (CVD), nano-imprinting,solvent thermal synthesis, nano-lithography, nano-casting, plasmaetching, and wet etching. Most of these nano-structuring methods areun-scalable, complicated, high-cost, and environmentally hazardous.

Therefore, a heretofore unaddressed need exists in the art to addressthe aforementioned deficiencies and inadequacies.

SUMMARY

In one aspect, the invention relates to a composite usably for oil-waterseparation. In one embodiment, the composite includes a nanostructuredpowder or porous material having surfaces with nanoscale features,formed from a pristine powder or porous material by a surfacenanostructuring process; and single or multilayers of one or more lowsurface energy oligomers, polymers, or their composites with othermaterials coated on the surfaces of the nanostructured powder or porousmaterial.

In one embodiment, the pristine powder or porous material comprises ametal, an alloy, a metal oxide, a compound of metals with non-metallicmaterials, a non-metallic material, an insulator, a conductor, asemiconductor, or a combination thereof.

In one embodiment, the one or more low surface energy oligomers,polymers, or their composites with other materials have surface energieslower than that of water and higher than that of oil. In one embodiment,the composite is hydrophobic (or superhydrophobic) and oleophilic (orsuperoleophilic) operably repelling water and absorbing oil.

In one embodiment, the one or more low surface energy oligomers,polymers, or their composites with other materials have surface energieslower than that of oil and higher than that of water. In one embodiment,the composite is oleophobic (or superoleophobic) and hydrophilic (orsuperhydrophilic) operably repelling oil and absorbing water.

In one embodiment, the surface nanostructuring process comprises a hotwater treatment (HWT) or steam treatment (ST) of the pristine powder orporous material.

In one embodiment, the single or multilayers of the low surface energyoligomer or polymer are coated on the surfaces of the nanostructuredpowder or porous material by a surface energy reduction processincluding solution immersion and oven evaporation.

In one embodiment, the single or multilayers of the low surface energyoligomer or polymer are coated on the surfaces of the nanostructuredpowder or porous material by chemical vapor deposition (CVD), physicalvapor deposition (PVD), pulsed laser deposition, evaporative deposition,sputter deposition, aerosol-assisted CVD, plasma enhanced CVD (PECVD),atomic layer deposition (ALD), spray coating, paintbrush, or spincoating.

In another aspect, the invention relates to a method of synthesizing acomposite usably for oil-water separation. In one embodiment, the methodincludes surface nanostructuring a pristine powder or porous material toform a nanostructured powder or porous material having surfaces withnanoscale features; and coating single or multilayers of one or more lowsurface energy oligomers, polymers, or their composites with othermaterials on the surfaces of the nanostructured powder or porousmaterial.

In one embodiment, the pristine powder or porous material comprises ametal, an alloy, a metal oxide, a compound of metals with non-metallicmaterials, a non-metallic material, an insulator, a conductor, asemiconductor, or a combination thereof.

In one embodiment, the one or more low surface energy oligomers,polymers, or their composites with other materials have surface energieslower than that of water and higher than that of oil. In one embodiment,the composite is hydrophobic (or superhydrophobic) and oleophilic (orsuperoleophilic) operably repelling water and absorbing oil.

In one embodiment, the one or more low surface energy oligomers,polymers, or their composites with other materials have surface energieslower than that of oil and higher than that of water. In one embodiment,the composite is oleophobic (or superoleophobic) and hydrophilic (orsuperhydrophilic) operably repelling oil and absorbing water.

In one embodiment, the surface nanostructuring process comprises a hotwater treatment (HWT) or steam treatment (ST) of the pristine powder orporous material.

In one embodiment, the HWT comprises mixing the powder or porousmaterial in water to form a mixture thereof and heating the mixture attemperatures higher than room temperature for a period of time to formthe nanostructured powder or porous material having the surfaces withnanoscale features.

In one embodiment, the ST comprises treating the powder or porousmaterial with steam for a period of time to form the nanostructuredpowder or porous material having the surfaces with nanoscale features.

In one embodiment, the HWT or ST is performed with the assistance ofmicrowave, infrared light heating, and/or in a high pressure container.

In one embodiment, the surface nanostructuring process comprises growingthe nanoscale features on the surfaces of the pristine powder or porousmaterial through a cross-deposition mechanism during the HWT. In oneembodiment, the cross-deposition mechanism comprises placing thepristine powder or porous material of a non-metallic powder or porousmaterial across a metal substrate during HWT, wherein molecules thatmigrate through water and deposit on the metal substrate to formnanostructures deposit on the neighboring non-metallic powder or porousmaterial and form a layer of HWT-nanostructures.

In one embodiment, the coating process is performed by a surface energyreduction process including solution immersion and oven evaporation.

In one embodiment, the coating process is performed by chemical vapordeposition (CVD), physical vapor deposition (PVD), pulsed laserdeposition, evaporative deposition, sputter deposition, aerosol-assistedCVD, plasma enhanced CVD (PECVD), atomic layer deposition (ALD), spraycoating, paintbrush, or spin coating.

In one embodiment, the method further includes, prior to the surfacenanostructuring process, a pretreatment process to activate the surfaceof the pristine powder or porous material, wherein the pretreatmentprocess includes acid dipping or plasma exposure.

In a further aspect, the invention relates to a filter usable foroil-water separation. In one embodiment, the filter includes a compositecomprising a nanostructured powder or porous material having surfaceswith nanoscale features, formed from a pristine powder or porousmaterial by a surface nanostructuring process; and single or multilayersof one or more low surface energy oligomers, polymers, or theircomposites with other materials coated on the surfaces of thenanostructured powder or porous material.

In one embodiment, the filter further includes a mesh frame holding thecomposite.

In one embodiment, the pristine powder or porous material comprises ametal, an alloy, a metal oxide, a compound of metals with non-metallicmaterials, a non-metallic material, an insulator, a conductor, asemiconductor, or a combination thereof.

In one embodiment, the one or more low surface energy oligomers,polymers, or their composites with other materials have surface energieslower than that of water and higher than that of oil. In one embodiment,the composite is hydrophobic (or superhydrophobic) and oleophilic (orsuperoleophilic) operably repelling water and absorbing oil.

In one embodiment, the one or more low surface energy oligomers,polymers, or their composites with other materials have surface energieslower than that of oil and higher than that of water. In one embodiment,the composite is oleophobic (or superoleophobic) and hydrophilic (orsuperhydrophilic) operably repelling oil and absorbing water.

In one aspect, the invention relates to an apparatus for oil-waterseparation. In one embodiment, the apparatus comprises the filter asdisclosed above; and a vacuum pump in fluid communication with thefilter for continuous oil-water separation.

In one embodiment, the filter is re-cyclically usable.

These and other aspects of the invention will become apparent from thefollowing description of the preferred embodiment taken in conjunctionwith the following drawings, although variations and modificationstherein may be affected without departing from the spirit and scope ofthe novel concepts of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings illustrate one or more embodiments of theinvention and, together with the written description, serve to explainthe principles of the invention. Wherever possible, the same referencenumbers are used throughout the drawings to refer to the same or likeelements of an embodiment.

FIG. 1 shows schematically processes of producing a functionalnanostructured powder/porous material with special wettability andapplication of the same, according to embodiments of the invention.

FIG. 2A shows schematically surface nanostructuring by hot watertreatment or steam treatment process, according to embodiments of theinvention.

FIG. 2 2B shows schematically surface energy reduction using immersionor evaporation process, according to embodiments of the invention.

FIG. 3 shows schematically applications of functional nanostructuredmetallic powders with special wettability in oil-water separation,according to embodiments of the invention.

FIG. 4 shows schematically nanostructured metal powder fabrication byhot water treatment (HWT), according to one embodiment of the invention.

FIG. 5 shows schematically nanostructured metal powder fabrication bysteam treatment (ST), according to one embodiment of the invention.

FIG. 6 shows schematically representation of nanostructured metallicpowder surface after the HWT or ST surface nanostructuring process,according to one embodiment of the invention.

FIG. 7 shows schematically a surface energy reduction process of thenanostructure metal powders by coating the powder surface with alow-surface-energy chemical using liquid immersion method, according toone embodiment of the invention.

FIG. 8 shows schematically a surface energy reduction process of thenanostructure metal powders by coating the powder surface with alow-surface-energy chemical using oven evaporation, according to oneembodiment of the invention.

FIG. 9 shows schematically a surface energy reduction process andnanostructured metallic powder surface by coating nanoscale featureswith low surface energy polymers, according to one embodiment of theinvention.

FIGS. 10A-10H show SEM images of Al (FIGS. 10A-10B), Mg (FIGS. 10C-10D),Zn FIGS. 10E-10F), and Cu (FIGS. 10G-10H) before (left column) and after(right column) after HWT process at 75° C., according to embodiments ofthe invention. Treatment times were 10, 20, 40 min and 24 hrs for Al,Mg, Zn, and Cu, respectively, in order to form well defined metal oxidenanostructures.

FIG. 11 shows growth of aluminum oxide nanostructures on Al surfaceafter 10 min of ST, according to one embodiment of the invention. Al hasbeen chosen as an example base metal; and nanostructure formation by theST can apply to a wide variety of metallic materials.

FIGS. 12A-12C show respectively images of pristine HWT-Al powders(superhydrophilic), functional HWT-Al powders (superhydrophobic), andtheir mixture after pouring the powder on water, according to oneembodiment of the invention

FIGS. 13A-13B show respectively images of a water droplet on functionalHWT-powders of Cu (FIG. 13A) and Mg (FIG. 13B), according to embodimentsof the invention.

FIGS. 13C-13D show respectively images of droplets of water, cyclohexane(dyed with oil red O), petroleum hydrocarbons on functional HWT-powdersof Zn (FIG. 13C), and Al (FIG. 13D), according to embodiments of theinvention.

FIGS. 14A-14D show respectively an oil-water separation filter module(FIG. 14A) and its application in separation of cyclohexane from water(FIGS. 14B-14D), according to one embodiment of the invention.Cyclohexane permeates through while tap water maintains above theseparation apparatus after 20 s. FIG. 14C shows oil collected afterseparation, while FIG. 14D shows oil-water mixture before separation.

FIGS. 15A-15C show respectively an oil-water separation filter module(FIG. 15A) and its application in oil-water separation (FIGS. 14B-14C),according to one embodiment of the invention. FIG. 15B shows oil-watermixture before separation, and FIG. 15C shows oil (petroleumhydrocarbons) collected after separation.

FIGS. 16A-16C show schematically a cartridge filter for continuousoil-water separation, according to one embodiment of the invention. FIG.16A shows a schematic diagram of the cartridge filter, and FIGS. 16B and16C shows a top-view and a side-view of the built cartridge filter,respectively.

FIG. 17 shows an apparatus equipped with a vacuum pump used forcontinuous oil-water separation, according to one embodiment of theinvention. The separation module (cartridge filter) was place into theoil-water mixture.

FIGS. 18A-18C shows respectively oil-water separation efficiency of afunctional HWT-Al-powder cartridge filter, separation efficiency of thecartridge filter after several cycles of separation, and separationefficiency of the cartridge filter after long time periods of continuousoil-water separation, according to one embodiment of the invention.

DETAILED DESCRIPTION

The invention will now be described more fully hereinafter withreference to the accompanying drawings, in which exemplary embodimentsof the invention are shown. This invention may, however, be embodied inmany different forms and should not be construed as limited to theembodiments set forth herein. Rather, these embodiments are provided sothat this disclosure will be thorough and complete, and will fullyconvey the scope of the invention to those skilled in the art. Likereference numerals refer to like elements throughout. Variousmodifications to these aspects will be readily apparent to those skilledin the art, and the generic principles defined herein may be applied toother aspects. Thus, the claims are not intended to be limited to theaspects shown herein, but is to be accorded the full scope consistentwith the language claims, wherein reference to an element in thesingular is not intended to mean “one and only one” unless specificallyso stated, but rather “one or more”. The word “exemplary” is used hereinto mean “serving as an example, instance, or illustration”. Any aspectdescribed herein as “exemplary” is not necessarily to be construed aspreferred or advantageous over other aspects. Unless specifically statedotherwise, the term “some” refers to one or more. Combinations such as“at least one of A, B, or C”, “one or more of A, B, or C”, “at least oneof A, B, and C”, “one or more of A, B, and C”, and “A, B, C, or anycombination thereof” include any combination of A, B, and/or C, and mayinclude multiples of A, multiples of B, or multiples of C. Specifically,combinations such as “at least one of A, B, or C”, “one or more of A, B,or C”, “at least one of A, B, and C”, “one or more of A, B, and C”, and“A, B, C, or any combination thereof” may be A only, B only, C only, Aand B, A and C, B and C, or A and B and C, where any such combinationsmay contain one or more member or members of A, B, or C. All structuraland functional equivalents to the elements of the various aspectsdescribed throughout this disclosure that are known or later come to beknown to those of ordinary skill in the art are expressly incorporatedherein by reference and are intended to be encompassed by the claims.Moreover, nothing disclosed herein is intended to be dedicated to thepublic regardless of whether such disclosure is explicitly recited inthe claims. The words “module”, “mechanism”, “element”, “device” and thelike may not be a substitute for the word “means”. As such, no claimelement is to be construed as a means plus function unless the elementis expressly recited using the phrase “means for”. It should also beunderstood that one or more steps within a method may be executed indifferent order (or concurrently) without altering the principles of theinvention.

The terms used in this specification generally have their ordinarymeanings in the art, within the context of the invention, and in thespecific context where each term is used. Certain terms that are used todescribe the invention are discussed below, or elsewhere in thespecification, to provide additional guidance to the practitionerregarding the description of the invention. For convenience, certainterms may be highlighted, for example using italics and/or quotationmarks. The use of highlighting has no influence on the scope and meaningof a term; the scope and meaning of a term are the same, in the samecontext, whether or not it is highlighted. It will be appreciated thatthe same thing can be said in more than one way. Consequently,alternative language and synonyms may be used for any one or more of theterms discussed herein, nor is any special significance to be placedupon whether or not a term is elaborated or discussed herein. Synonymsfor certain terms are provided. A recital of one or more synonyms doesnot exclude the use of other synonyms. The use of examples anywhere inthis specification including examples of any terms discussed herein isillustrative only, and in no way limits the scope and meaning of theinvention or of any exemplified term. Likewise, the invention is notlimited to various embodiments given in this specification.

It will be understood that when an element is referred to as being “on”,“attached” to, “connected” to, “coupled” with, “contacting”, etc.,another element, it can be directly on, attached to, connected to,coupled with or contacting the other element or intervening elements mayalso be present. In contrast, when an element is referred to as being,for example, “directly on”, “directly attached” to, “directly connected”to, “directly coupled” with or “directly contacting” another element,there are no intervening elements present. It will also be appreciatedby those of skill in the art that references to a structure or featurethat is disposed “adjacent” to another feature may have portions thatoverlap or underlie the adjacent feature.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the disclosure.As used herein, the singular forms “a”, “an” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise. It will be further understood that the terms “comprises”and/or “comprising”, or “includes” and/or “including” or “has” and/or“having” when used in this specification specify the presence of statedfeatures, regions, integers, steps, operations, elements, and/orcomponents, but do not preclude the presence or addition of one or moreother features, regions, integers, steps, operations, elements,components, and/or groups thereof.

It will be understood that, although the terms first, second, third,etc. may be used herein to describe various elements, components,regions, layers and/or sections, these elements, components, regions,layers and/or sections should not be limited by these terms. These termsare only used to distinguish one element, component, region, layer orsection from another element, component, region, layer or section. Thus,a first element, component, region, layer or section discussed below canbe termed a second element, component, region, layer or section withoutdeparting from the teachings of the disclosure.

Furthermore, relative terms, such as “lower” or “bottom” and “upper” or“top”, may be used herein to describe one element's relationship toanother element as illustrated in the figures. It will be understoodthat relative terms are intended to encompass different orientations ofthe device in addition to the orientation shown in the figures. Forexample, if the device in one of the figures is turned over, elementsdescribed as being on the “lower” side of other elements would then beoriented on the “upper” sides of the other elements. The exemplary term“lower” can, therefore, encompass both an orientation of lower andupper, depending on the particular orientation of the figure. Similarly,if the device in one of the figures is turned over, elements describedas “below” or “beneath” other elements would then be oriented “above”the other elements. The exemplary terms “below” or “beneath” can,therefore, encompass both an orientation of above and below.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this invention belongs. It will befurther understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art and thepresent disclosure, and will not be interpreted in an idealized oroverly formal sense unless expressly so defined herein.

As used herein, the terms “comprise” or “comprising”, “include” or“including”, “carry” or “carrying”, “has/have” or “having”, “contain” or“containing”, “involve” or “involving” and the like are to be understoodto be open-ended, i.e., to mean including but not limited to.

Typically, terms such as “about,” “approximately,” “generally,”“substantially,” and the like unless otherwise indicated mean within 20percent, preferably within 10 percent, preferably within 5 percent, andeven more preferably within 3 percent of a given value or range.Numerical quantities given herein are approximate, meaning that the term“about,” “approximately,” “generally,” or “substantially” can beinferred if not expressly stated.

Typically, “nanoscopic-scale,” “nanoscopic,” “nanometer-scale,”“nanoscale,” the “nano-” prefix, and the like refers to elements orarticles having widths or diameters of less than about 1 μm, preferablyless than about 100 nm in some cases. Specified widths can be smallestwidth (i.e. a width as specified where, at that location, the articlecan have a larger width in a different dimension), or largest width(i.e., where, at that location, the article's width is no wider than asspecified, but can have a length that is greater), unless pointed outotherwise.

The description is now made as to the embodiments of the invention inconjunction with the accompanying drawings. It should be understood thatspecific embodiments described herein are merely intended to explain theinvention, but not intended to limit the invention. Variousmodifications to these aspects will be readily apparent to those skilledin the art, and the generic principles defined herein may be applied toother aspects. In accordance with the purposes of this invention, asembodied and broadly described herein, this invention relates to acomposite for oil-water separation, synthesis methods and applicationsof the same.

In certain embodiments, the composite includes a nanostructured powderor porous material having surfaces with nanoscale features, formed froma pristine powder or porous material by a surface nanostructuringprocess; and single or multilayers of low surface energy oligomers,polymers, or their composites with other materials coated on thesurfaces of the nanostructured powder or porous material.

In certain embodiments, the pristine powder or porous material comprisesa metal, an alloy, a metal oxide, a compound of metals with non-metallicmaterials, a non-metallic material, an insulator, a conductor, asemiconductor, or a combination thereof.

In certain embodiments, the low surface energy oligomers, polymers, ortheir composites with other materials have surface energies lower thanthat of water and higher than that of oil. In one embodiment, thecomposite is hydrophobic (or superhydrophobic) and oleophilic (orsuperoleophilic) operably repelling water and absorbing oil.

In certain embodiments, the low surface energy oligomers, polymers, ortheir composites with other materials have surface energies lower thanthat of oil and higher than that of water. In one embodiment, thecomposite is oleophobic (or superoleophobic) and hydrophilic (orsuperhydrophilic) operably repelling oil and absorbing water.

In another aspect, the invention relates to a method of synthesizing acomposite usably for oil-water separation. In some embodiments, themethod includes surface nanostructuring a pristine powder or porousmaterial to form a nanostructured powder or porous material havingsurfaces with nanoscale features; and coating single or multilayers of alow surface energy oligomer or polymer on the surfaces of thenanostructured powder or porous material.

In some embodiments, the surface nanostructuring process comprises a hotwater treatment (HWT) or steam treatment (ST) of the pristine powder orporous material.

In some embodiments, the HWT comprises mixing the powder or porousmaterial in water to form a mixture thereof; and heating the mixture attemperatures higher than room temperature for a period of time to formthe nanostructured powder or porous material having the surfaces withnanoscale features.

In some embodiments, the ST comprises treating the powder or porousmaterial with steam for a period of time to form the nanostructuredpowder or porous material having the surfaces with nanoscale features.

In some embodiments, the HWT or ST is performed with the assistance ofmicrowave, infrared light heating, and/or in a high pressure container.

In some embodiments, the surface nanostructuring process comprisesgrowing the nanoscale features on the surfaces of the pristine powder orporous material through a cross-deposition mechanism during the HWT. Insome embodiments, the cross-deposition mechanism comprises placing thepristine powder or porous material of a non-metallic powder or porousmaterial across a metal substrate during HWT, wherein molecules thatmigrate through water and deposit on the metal substrate to formnanostructures deposit on the neighboring non-metallic powder or porousmaterial and form a layer of HWT-nanostructures.

In some embodiments, the coating process is performed by a surfaceenergy reduction process including solution immersion and ovenevaporation.

In some embodiments, the coating process is performed by chemical vapordeposition (CVD), physical vapor deposition (PVD), pulsed laserdeposition, evaporative deposition, sputter deposition, aerosol-assistedCVD, plasma enhanced CVD (PECVD), atomic layer deposition (ALD), spraycoating, paintbrush, or spin coating.

In some embodiments, the method further includes, prior to the surfacenanostructuring process, a pretreatment process to activate the surfaceof the pristine powder or porous material, wherein the pretreatmentprocess includes acid dipping or plasma exposure.

One aspect of the invention also relates to a new approach of oil-waterseparation by powder or porous materials with nanostructured metal oxidesurface that is synthesized by hot water processes. The overallfabrication and operation of the oil-water separator is low-cost andscalable. In addition, metal oxides also provide stronger adhesion withthe surface chemicals and provide superior wetting durability. Thefabrication process involves surface nanostructuring by a hot waterprocess followed by a chemical treatment for surface energy reduction.For example, one approach is that metallic powders or foams developmetal oxide nanostructures on their surface after being immersed in hotwater or exposed to steam. Then it is coated with a low surface energyself-assembled monolayer (SAM) oligomer or polymer, also by simplemethods such as immersion, in order to acquire superhydrophobicity andoleophilicity. If the material comprises micro-scale features, the finalmorphology achieves a hierarchical micro-nano-roughness that furtherenhances the wetting properties. Such powder/porous material withspecial wettability is enclosed within a filter geometry and separatethe pumped oil-water mixture. Especially, powder material still retainsits wetting properties after being mold into almost any shape, whichleads to the design of new filter modules with desired size and shape.Powder-based filters also have the advantage of easy cleaning andre-usability. These make it an easy implementation of such filters tothe existing oil-water separation technologies.

In certain embodiments, modified hot water treatment processes are usedto coat non-metallic powder/porous materials with metal oxidenanostructures. This allows the applicability of the invention to a widevariety of base powder/porous material types. Furthermore, there areother material geometries and wetting situations that can be used foroil-water separation using the hot water process of this invention.

In certain aspects, the invention relates to powder and porous materialsfor oil-water separation synthesized by chemical surface modificationprocesses, which reduce the surface energy of a given material. Incertain embodiments, the chemical surface modification mainly involveslow-surface energy polymer coated on the base material as aself-assembled monolayer. In general, the surface chemistry is essentialfor a material to acquire special wettability, and usually its surfaceenergy is reduced to sufficiently lower energies compared to a certainliquid and becomes “-phobic” towards that liquid. For example, Teflonhas a lower surface energy than water and is hydrophobic. On thecontrary, if the surface energy of the material is higher compared tothat of the liquid, it becomes “-philic” toward that liquid. As anexample, most of the oxide materials have relatively higher surfaceenergies compared to oil and they show an oleophilic behavior. Inaddition to the surface chemistry, morphology can enhance thewettability of a solid surface. A material can be made to besuperhydrophobic from hydrophobic or superhydrophilic from hydrophilicafter modifying the surface morphology. An example of the surfacemorphology effect on its wettability is when a nanostructured layer isformed prior to surface energy reduction. The higher surface area of thenano-rough surface compared to a planar one can improve the wettingbehavior of the material, which has been proposed also for oil-waterseparation applications. Multiscale roughened surfaces (e.g.hierarchically structured) can further enhance the wetting properties,and for example can make a hydrophobic/oleophobic materialultra-hydrophobic or ultra-oleophobic. For oil-water separationpurposes, skeletal porous materials, often called “frame”, withmicro-scale features such as mesh, foam, sponge, and membranes can gainhierarchical surface morphology when a nanostructured layer is introduceon the micro-scale features.

Certain aspects of the invention relates to the fabrication/synthesis ofpowder or porous materials (metallic and non-metallic) with specialwettability for continuous, high efficiency, and long term oil-waterseparation at very low fabrication and operation cost. The materials(powder or porous) include surface-nanostructured materials and posesspecial wettability using a combination of chemical and physical surfacemodification processes. The surface modification processes used aresimple, low-cost, scalable, high-throughput, and eco-friendly, whichovercome most of the limitations of conventional surface modificationprocesses.

In certain embodiments, the physical surface modification is based on alow-temperature nanostructure fabrication method and does not requireany special environments/steps such as vacuum, acidic/alkalinesolutions, or lithographical processing.

In certain embodiments, the chemical surface modification involves asimple immersion process of nanostructured surface into an energyself-assembled monolayer (SAM) oligomer or polymer solution to reducetheir surface energy.

In certain embodiments, the resultant materials have different types ofspecial wettability such as the hydrophobicity (or superhydrophobicity)and oleophilicity (or superoleophilicity) (repelling water and absorbingoil), or the oleophobicity or superoleophobicity and hydrophilicity orsuperhydrophilicity (repelling oil and absorbing water). In certainembodiments, the nanostructuring surface processes form a nanostructuredmetal oxide layer on a base powder or porous material. The methods areapplicable to a wide variety of powder or porous materials includingthose made of elemental metal, alloy metals, or compound metals orcombination of them with other non-metallic powders.

FIG. 1 is a schematic diagram of the approach according to oneembodiment of this invention. First, morphology of the baseporous/powder material is changed by a hot water process to acquirenanoscale features. Then, it is followed by a chemical surface energyreduction step to achieve special wettability towards water and oil. Incertain embodiments, the oil/water separator is made of those materialsthat are capable to separate oils from water in oil spills or othertypes of oil polluted water.

FIGS. 2A and 2B illustrate respectively the physical and chemicalsurface modification processes according to embodiments of thisinvention. The surface nanostructuring step, which is a physical surfacemodification, can be achieved using any of the two simple nanostructurefabrication techniques: hot water treatment or steam treatment. Surfaceenergy reduction step, which is a chemical surface modification, can beachieved either by immersing the nanostructured material in alow-surface-energy solution or evaporating the solution in oven to coatthe nanostructured surface.

As a result of the physical and chemical surface modification processes,powder or porous materials demonstrate special wettability towardliquids of different surface energy such as water and oils. In certainembodiments, the materials fabricated have either hydrophobicity (orsuperhydrophobicity) and oleophilicity (or superoleophilicity), orhydrophilicity (or superhydrophilicity) and oleophobicity (orsuperoleophoboicity) depending on the low-surface-energy chemicals usedin the chemical surface modification step, as shown in FIG. 2B. Overall,the materials can either repel water and absorb oils, or absorb waterand repels oils, which can be utilized to separate oils from water(oil-water separation) when a mixture of water and oil poured on thepowder/porous material. As an example, FIG. 3 represents how a powdermaterial prepared by the approach is used in oil-water separation. Thepowder material is either a superhydrophobic/superoleophilic material330 (left-hand side of the oil-water separation), or asuperhydrophilic/superoleophobic material 335 (right-hand side of theoil-water separation).

Certain aspects of the invention also relate to a filter usable foroil-water separation, as shown in FIGS. 14A-14D and 15A-15C. In someembodiments, the filter includes a composite comprising a nanostructuredpowder or porous material having surfaces with nanoscale features,formed from a pristine powder or porous material by a surfacenanostructuring process; and single or multilayers of a low surfaceenergy oligomer or polymer coated on the surfaces of the nanostructuredpowder or porous material.

In some embodiments, the filter further includes a mesh frame holdingthe composite.

Certain aspects of the invention also provide an apparatus for oil-waterseparation, as shown in FIGS. 16SA-16C and 17 . In some embodiments, theapparatus comprises the filter as disclosed above; and a vacuum pump influid communication with the filter for continuous oil-water separation.

In some embodiments, the filter is re-cyclically usable.

Without intent to limit the scope of the invention, examples and theirrelated results according to the embodiments of the present inventionare given below. Note that titles or subtitles may be used in theexamples for convenience of a reader, which in no way should limit thescope of the invention. Moreover, certain theories are proposed anddisclosed herein; however, in no way they, whether they are right orwrong, should limit the scope of the invention so long as the inventionis practiced according to the invention without regard for anyparticular theory or scheme of action.

Surface Nanostructuring (Physical Surface Modification):

According to the invention, two methods are used to introduce nanoscalefeatures into the surface of powder or porous materials, as shown inFIG. 2A: hot water treatment (HWT) and steam treatment (ST). Those twomethods are both based on the reaction between hot water with themetallic surface of materials to synthesize metal oxide nanostructureswithout the need to any types of complicated or expensive fabricationconditions/equipment. In the case of HWT, the metal is directly immersedin hot water, while for the ST, steam first condenses on the surface ofthe metal, forms hot water droplets, and reacts with the metal. Each hasits own advantages. Overall, the HWT is a simpler single-step process.On the other hand, the ST can provide temperatures beyond the boilingpoint of water, enhance the kinetics, and therefore shorten thetreatment time. ST can also be more scalable in treating industrialamount and size of materials.

Below is a detailed description on the HWT and ST methods and how metaloxide nanostructures grow on the powder or porous material surfaces. Itis followed by a description on two simple surface energy reductionprocess, solution immersion and oven evaporation, to reduce the surfaceenergy on nanostructured surface.

Hot Water Treatment (HWT): Referring to FIG. 4 , the hot water treatmentprocess is shown according to one embodiment of the invention, whichinvolves a reaction between metal powder particles 410 and water 420,e.g., deionized (DI) water, distilled water, purified water, or anyother types of water, at temperatures higher than room temperature,typically between 40-100° C. According to the invention, any types ofheating devices, e.g., a range 401, can be used to heat the water 420.The reaction of the hot water 420 and the metal powder particles 410results in nanostructured metal powder particles 430 having rough metaloxide surfaces with features in the nanoscale (nanostructured metaloxide) approximately in the range of 25-500 nm on the surface of thebase metal powder particles 410. Nanostructures formed by the HWTprovide significantly rough surfaces compared to a pristine material.Previously, the process has mainly been used to fabricate metal oxidethin films (e.g., MgO, ZnO, CuO, and Al₂O₃) [10-13_ENREF_10]. The HWTprocess is a simple and eco-friendly process, does not involve anychemicals, such as surfactants, reductants, oxidation agents, additivesor any byproducts, and also takes place at relativity low temperatures.Since no complicated fabrication processes are involved in the HWT, suchas the need for vacuum environment or plasma, the HWT process islow-cost, scalable, and high-throughput.

Steam Treatment (ST): As a faster and more scalable alternative to theHWT, steam treatment can effectively form metal oxide nanostructures onsurfaces of a powder or porous material, as shown in FIG. 5 . In thisexemplary embodiment, nanostructured metal powder particles 530 areformed after metal powder particles (powder or porous material) 510 aretreated by the steam 520. Different from the HWT, which is limited tothe maximum boiling temperature of water, during the ST, water isdelivered to the surfaces of the powder or porous material in the formof vapor that can acquire almost any temperature. Higher temperatures ofthe steam allow much faster nanostructure formation kinetics. Steam alsodoes not require the use of high purity or DI water. Regular tap watercan be evaporated to produce a steam that is free from impurities.During the ST, molecular oxygen from the ambient environment isincorporated to the steam that further increases the nanostructureformation kinetics. In addition, the ST allows spatial control onnanostructuring and easy patterning. For example, using a beam of steamcoming out of a nozzle, one can do the ST on selected regions of a givenmetal and form a heterogeneous pattern incorporating untreated metal andST metal oxide nanostructures. Other than these differences, the ST hasall the advantages and similar nanostructure properties of the HWTsurfaces described above.

FIG. 6 is an illustrative representation of a powder, as an example of apowder or porous material according to one embodiment of the invention,and shows the change in its morphology resulting from surfacenanostructuring by the HWT or ST process. Compared to the pristinematerial 610, the particle 630 treated with hot water (HWT or ST) has arough surface including nanoscale features. The nanoscale roughness is avery essential for a surface to acquire the special wettability after asurface energy reduction step. The HWT and ST, as a method to producenanoscale features, are a very good fit for roughening materials surfaceto produce oil/water separator materials as they are very simple andfacile processes.

Surface Energy Reduction (Chemical Surface Modification):

In certain embodiments, chemical surface modification approaches such asintroducing thin or thick layers, single or multilayers of low surfaceenergy oligomers/polymers on a base material using liquid or vaporcoating techniques are used to reduce the surface energy of powders orporous materials and achieve the special wettability property. Reducingthe surface energy of a surface is the key factor in fabricatingmaterials with special wettability for oil/water separation. The surfaceshould have a surface energy lower than water and higher than oils inorder to separate the water and old from an oil/water mixture. Accordingto the invention, very simple chemical surface modification techniquesare used to coat the surface of materials with a single thin layer oflow surface energy chemicals. FIGS. 7 and 8 schematically show twoapproaches of the chemical surface modification: solution immersion andoven evaporation, respectively, to coat the surface of materials with asingle thin layer of low surface energy chemicals. In the approach ofthe solution immersion, as shown in FIG. 7 , the nanostructured metalpowder particles 710 is immersed in a solution 720 of alow-surface-energy chemical and functional nanostructured metal powderparticles 730 are then formed by coating the powder surface with thelow-surface-energy chemical. The resulted have special wettability. FIG.8 shows a schematic of the oven evaporation approach to coat the surfaceof materials with a single thin layer of low surface energy chemicals,where the nanostructured metal powder particles 810 and a solution 820of a low-surface-energy chemical are disposed in an oven 801, and areheated therein to evaporate the low-surface-energy chemical solution820. The evaporation of the low-surface-energy chemical condenses on thesurfaces of the nanostructured metal powder particles 810 to formfunctional nanostructured powder particles 830 with special wettability.It should be appreciated that a porous material such as mesh or foam canalso be used to practice the invention.

Furthermore, other surface energy reduction methods can also be used tocoat the surfaces of powder or porous materials with a single thin layerof low surface energy chemicals with special wettability. As an exampleillustrated in FIG. 9 , nanostructured metallic powder particles 910 arechemically modified to obtain functional nanostructured powder particles930 having a lower surface energy by being coated with a self-assembledmonolayer (SAM) polymer 930 that leads to change in their surfacewettability toward different liquids. For metallic powder with specialwettability, reducing their surface energy can bring the surface tobecome hydrophobic (or superhydrophobic) and oleophilic (orsuperoleophilic).

Results and Discussions:

In certain aspects of the invention, the simple nanostructure synthesistechniques (hot water treatment, steam treatment) and surface energyreduction methods (solution immersion, oven evaporation) are used togenerate powder or porous materials with special wettability foroil-water separation applications. All the methods described above arefacile, low-cost, scalable, and eco-friendly. As an example, metallicpowder was chosen to demonstrate the physical and chemical surfacechanges involved and its special wettability toward water and oil.Certain aspects of the invention also relate to an oil-water separationapparatus comprising the functionalized powder or porous materials.

In certain embodiments, nanostructuring powder or porous materials areformed by the HWT or ST. During these hot water processes, surfaces of agiven powder or porous metallic material react with water attemperatures higher than room temperature (typically >50° C.) to formnanostructured metal oxides [10, 11, 14-18]. In order to introduce ananostructured layer onto a metal powder surface, potentialcontamination on the powder surfaces is removed by ultrasonicating thepowders first with acetone, isopropanol, and DI water each for about 5min, and then dried. For the HWT, cleaned metal powders are thenimmersed in hot DI water as shown in FIG. 4 . Treatment time may varydepending on the metal; basically it ranges between a few minutes up toseveral hours or days. In some embodiments, the morphology of thenanostructured layer on a metal powder can be tuned by varying theimmersion time (from a few minutes up to several hours or days). FIGS.10A-10H show the scanning electron microscopy (SEM) images of aluminum(FIGS. 10A-10B), magnesium (FIGS. 10C-10D), zinc (FIGS. 10E-10F), andcopper (FIGS. 10G-10H) metal powder surfaces before (FIGS. 10A, 10C, 10Eand 10G) and after (FIGS. 10B, 10D, 10F and 10H) the HWT at 75° C. TheSEM images show the formation of nanoscale features (nanostructuredmetal oxide) on the respected metal powder after the HWT, which does notexist before the HWT process. All powder surfaces show the formation ofnanoscale features and distributed uniformly on metal powder surfaces,such as aluminum oxide nanograss on Al powders, zinc oxide nanowires onZn powders, and nanoplates for Cu in a plate-like shape in the scale ofa few of nanometers.

As illustrated in FIG. 5 , for the ST, similar to the HWT approach, whenclean metal powder surfaces are exposed to water steam (vapor) for acertain time period (depending on the type of metals), metal powdersurfaces react with gaseous water molecules and oxidize the surfaces.The oxidized metal ions redeposit on metal surfaces again by migrationthrough condensed hot water and form metal oxide nanostructures. Sizesof ST-nanostructures can vary from few tens of nanometers up to severalhundreds of nanometers, as shown in FIG. 11 . Because this processinvolves the reaction between water vapor and the metal powder surfaces,the ST process takes place in a much faster when compared to the HWT,since water vapor can reach to much higher temperatures compared to hotliquid water (i.e., limited to boiling temperature) and thus thekinetics of metal oxide nanostructure growth becomes enhanced.

In certain embodiments, to obtain metal powders of special wettability,nanostructured powders were coated with low surface energy materialsusing self-assembled monolayer (SAM) polymer. In one embodiment,HWT-powders were dispersed in 20 ml hexane, and 0.01 g of 1H, 1H, 2H,2H-perfluorodecyltrichlorosilane (FDTS) or 10 mM of 1-Dodecanethiol(DDT), as illustrated in FIG. 7 . The solution was gently stirred atambient temperature for a set period of time depending on the metalused. The powder was then dried overnight at the ambient environment toobtain the functional metal powder particles. As shown in FIG. 12B, whenthe powders are poured on water, the functional metal powders floated onthe water surface without sinking due to its strong water-repellingproperty (superhydrophobic). On the other hand, as shown in FIG. 12A,the pristine HWT-nanostructured metal powders (without chemicaltreatment) sank underwater because of its strong water-attractingproperty (superhydrophilic). When a mixture of HWT-Al powder andfunctional one were mixed with water, after slight stirring the HWT-Alpowders sank under water and the functional one remained on the watersurface, as shown in FIG. 12C. Similar to Al, other metal powders (Cu,Zn, Mg, etc.) also showed superhydrophilic property after the HWT andsuperhydrophobic property for the functional HWT-powder after thechemical treatment.

In some embodiments, a small droplet of water with a volume of 10 μLappears to be a sphere on the superhydrophobic Cu (FIG. 13A) and Mg(FIG. 13B) functional powder surfaces. Among various droplets of waterand oils, cyclohexane (dyed with oil red O) and petroleum hydrocarbons,of about 10 μL placed on functional Al (FIG. 13C) and Zn (FIG. 13D)powders, the water droplet still have a sphere shape. On the other hand,oil droplets were absorbed by the powder materials. These resultsindicate the special wettability of functional metal powder havingsuperhydrophobic and superoleophilic behavior. In all the functionalpowder materials tested, a bright, reflectively visible surfaceunderneath the water droplet at the water-powder interface is observed,which indicates the existence of trapped air and the formation of acomposite solid-liquid-air interface that enhance the hydrophobicity ofa surface toward water.

For a quantitative surface wettability analysis, a sessile drop methodwas used to measure the contact angles (CAs) of water and oils on ourpowder materials. 5 μL of water and oil were placed on a flattenedfunctional HWT-powder and CA was measured on five different positions onthe surface. The average of contact angle values for water and differentoils are listed in Table 1. As discussed before, the formation ofcomposite solid-liquid-air interface enhances the surfacesuper-repellence toward water. A high water contact angle (WCA) of about163° was achieved on functional HWT-Cu-powders. WCAs for other materialswere also high with about 158°, 157°, and 151° for Zn, Al, and Mgfunctional HWT-powders, respectively. On the contrary, the petroleumhydrocarbons and cyclohexane droplet can wet the superhydrophobicsurface completely and spread out the surface immediately, within thetime of 0.5 s, as shown in FIGS. 13C and 13D for Al and Zn. In otherwords, their oil contact angles (OCAs) can be assumed to be about 0°,which indicates the desired superhydrophobic/superoleophilic specialwetting property for oil-water separation applications. For functionalHWT-Mg-powder, OCA was about 18° for cyclohexane (died with red) and 22°for petroleum hydrocarbons, which still provides a special wettingproperty of superhydrophobic/oleophilic behavior.

TABLE 1 Contact angle of water and oils on functional HWT-powders.Functional HWT-Powder Contact Angle (Degrees) Liquid Cu Zn Al Mg Water163 158 157 151 Cyclohexane 0 0 0 18 Petroleum hydrocarbons 0 0 0 22

With the special wettability of the functional HWT-powder surface,superhydrophobic and superoleophilic properties simultaneously, itbecomes an ideal candidate for removing oil from water in an oil-watermixture. Oil gets absorbed instantaneously when it is brought intocontact with a functional HWT-powder surface, while water remains on thesurface resulting in a separating process. More importantly, all the oilabsorbed in the powders can be easily and very quickly removed byrinsing the oil-saturated powder with acetone and can be reused foroil-water separation several times.

In one aspect, the invention relates to an oil-water separationfilter/apparatus. In one embodiment shown in FIGS. 14-14D, module (FIG.14A) including the 2.5 g of functional HWT-Al powders and cotton fixedinto a funnel end, is used to separate a cyclohexane-water mixture. Asshown in FIG. 14B, when the mixture of tap water solution andcyclohexane (25 ml, dyed with oil red O) (FIG. 14D) was poured onto thefunnel filter, the cyclohexane was absorbed by the powders, penetratedthe filter, and flowed down the beaker beneath (FIG. 14C); whereas, thetap water retained on the surface of the metal powders (FIG. 14B). Inanother embodiment, an identical filter module was used for separationof tap water (water was dyed with methylene blue) and 25 ml of petroleumhydrocarbons. As shown in FIG. 15B, the apparatus worked successfully,where water remained on the surface of the metal powder (FIG. 15A) andall the oil got absorbed by the powders and collected in the beakerunderneath the filter (FIG. 15C).

Afterwards, another filter design was used for continuous oil-waterseparation and handling larger quantities of oil-water mixture. FIG. 16Ashow a prototype cartridge filter module built using pristine Cu mesh tohold the functional HWT-powders in a cylindrical shape, a reservoir tocollect the separated oil, and a vacuum pump to pump the oil out (FIG.17 ). In one embodiment, about 100 gm of the functional HWT-Zn powdersplaced into the filter cartridge and placed in a 1000 ml of tap watersuch that half of the cartridge powders were in contact with water.Then, 100 ml of cyclohexane (dyed with oil red O) was poured onto thebeaker to get the oil-water mixture for separation. The Cu mesh has ahydrophobic and oleophilic property and the functional HWT-Zn-powder hada superhydrophobic and superoleophilic surface property, which absorbsthe oil very quickly while not letting the water in. When the oil waspoured into the tap water beaker, the oil quickly began to be absorbedby the powder with the help of vacuum pump. The total time forseparation of the oil-water mixture was merely about 1 min. No water wasobserved in the collected oil.

The separation efficiency of the prototype filter toward cyclohexane andpetroleum hydrocarbons is shown in FIG. 18A. The separation efficiencytoward the cyclohexane-water was close to 100%, while efficiency ofpetroleum hydrocarbons-water mixture was about 99.5%, as shown in FIG.18A. The total time for separation of the oil-water mixtures was about 5min for the first simple filtering module. Therefore, a vacuum pumpsystem is needed to speed up the filtration process time in order toexpand the application of using the functional HWT-powders in the fieldof oil-water separation.

Furthermore, the filtration process was applied to the filter manysuccessive cycles. It was observed that the filter can maintain its highseparation efficiency even after 200 cycles of oil-water separation, asshown in FIG. 18B. Importantly, the filter can retain its highseparation efficiency regards the continuous separation. FIG. 18C showsthe filter performance for different time periods of continuousoil-water separation. The results show the ability of the filter to doseparation after 120 min of continuous separation with very highefficiency. Also the filter durability was tested by performing acomplete filtration after several days. As shown in FIG. 18C, the filterremains its high separation efficiency even after 45 days from the firsttime of use. These proof-of-concept results indicate that functionalpowder/porous materials of this invention that have special wettabilitycan be good candidates in several oil-water separation applications suchas the treatment of oil-polluted water and oil-spill cleanup.

Alternatives for Surface Nanostructuring (Physical SurfaceModification): Water is the main element in physical surfacemodification methods of the HWT and ST, either of which can be used toachieve the surface nanostructuring of materials according to theinvention. In a typical HWT or ST process, water with high resistivity,low conductivity, and high purity is preferred. However, water of poorerqualities of these properties such as tap water, mineral water, or evenwater from lakes, rivers, and sea as an alternative can also be used forboth the HWT and ST and can further lower the fabrication costs ofnanostructuring step.

In addition, the kinetics of hot water process and thereforenanostructure growth rates can be enhanced by incorporatingtools/conditions that further enhance the effective temperature of thebase porous/powder material. For example, microwave (e.g.,microwave-assisted HWT), high pressure (HWT in a high pressurecontainer), and infrared light heating (IR-assisted ST or HWT) can beutilized during the hot water process according to the invention.

Alternatives for Surface Energy Reduction (Chemical SurfaceModification): Solution immersion and oven evaporation are the processesutilized in this invention to reduce the surface energy ofnanostructured materials. Several other surface energy reduction methodscan also be used for chemical surface modification after the physicalsurface modification step of this invention to fabricate materials withspecial wettability as described above. In general, thin film depositionmethods such chemical vapor deposition (CVD) or physical vapordeposition (PVD) can be used as alternative to solution immersion andoven evaporation processes. Pulsed laser deposition, evaporativedeposition, sputter deposition are some examples of PVD.Aerosol-assisted CVD, plasma enhanced CVD (PECVD), atomic layerdeposition (ALD) are some examples of CVD methods.

In addition, any chemicals that have low-energy functional group or canlead to a surface of lower energy can be used in this invention.

Hybrid Physical-Chemical Surface Modifications: In certain embodiments,powder nanostructures produced by the HWT or ST can be coated with lowsurface-energy chemicals, and deposited on the surface of porous basematerial by methods such as spray coating, paintbrush, or spin coating.

Alternative Base Materials: Metallic powder/porous materials of thisinvention, such as materials made of pure elemental metals, alloys, andcompounds are the best candidate materials that can directly acquire ananostructured surface as described above. In addition, any othercompositions made by combination of them with other non-metallicmaterials can also be used to form a nanostructured surface.

As another alternative, any type of powder/porous material includinginsulators, conductors, semiconductors can be coated with nanostructuresof the HWT or ST process through a cross-deposition mechanism. Forexample, a non-metallic porous material can be places across a metalplate during the HWT or ST. The molecules that migrate through water anddeposit on metal substrate to form nanostructures can also deposit onthe neighboring non-metallic porous material and can form a layer ofHWT-nanostructures.

Surface Activation Methods: In certain embodiments, nanostructureformation kinetics can be enhanced by activating the surface withpretreatment methods such as acid dipping (e.g., HF, HCL, HNO₃, and soon) or plasma exposure. Chemically modified metallic surfaces canincorporate higher number of metal ions that can speed up thefabrication process.

Briefly, aspects of the invention relates to a composite for oil-waterseparation, synthesis methods and applications of the same, which have,among other things, the following key features.

-   -   Oil-water separation can be performed by powder or porous        materials with nanostructured metal oxide surface that is        synthesized by a simple, low-cost, scalable, fast, and        environment-friendly hot water process.    -   Hot water process can produce a nanostructured metal oxide        surface on the base porous/powder material for physical surface        modification, which is followed by almost any type of chemical        surface modification in order to reduce the surface energy of        the nanostructured surface, and therefore leading to a special        wetting property for oil-water separation applications.    -   Special wettability of the surfaces produced by hot water        process and chemical surface modification can include surfaces        that can repel water (hydrophobic or superhydrophobic) and        absorb oils (oleophilic or superoleophilic), or materials that        can repel oils (oleophobic or superoleophobic) and absorb water        (hydrophilic or superhydrophilic).    -   Hot water process can be in the form of hot water treatment        (HWT) that produces a nanostructured surface on the base        porous/powder material, nanostructured surface can be chemically        modified by methods including solution immersion and oven        immersion, which at the end leads to powder/porous materials        with special wettability for oil-water separation applications.    -   Hot water process can be in the form of steam treatment (ST)        that produces a nanostructured surface on the base porous/powder        material, nanostructured surface can be chemically modified by        methods including solution immersion and oven immersion, which        at the end leads to powder/porous materials with special        wettability for oil-water separation applications.    -   Hot water process can be assisted with other tools/conditions,        including microwave (e.g., microwave-assisted HWT), high        pressure (HWT in a high pressure container), and infrared light        heating (IR-assisted ST or HWT), in order to enhance        kinetics/thermodynamics of the nanostructuring mechanisms on the        base porous/powder material, nanostructured surface can be        chemically modified by methods including solution immersion and        oven immersion, which at the end leads to powder/porous        materials with special wettability for oil-water separation        applications.    -   Hot water process can use a wide variety of water including DI        water and purified water, as well as water of poorer quality but        lower cost including tap water, mineral water, or even water        from lakes, rivers, and sea as alternatives, which further lower        the fabrication costs of nanostructuring step of this invention.    -   Surface energy reduction of the nanostructured surface produced        by hot water process can be achieved by a wide variety of        chemical energy modification methods including liquid immersion,        oven evaporation, microwave evaporation, and also thin film        deposition methods such chemical vapor deposition (CVD) or        physical vapor deposition (PVD).    -   Powder nanostructures produced by hot water process can be        coated with low surface-energy chemicals, and deposited on the        surface of porous/powder base material by methods such as spray        coating, paintbrush, or spin coating, which can directly provide        surfaces of special wettability for oil-water separation.    -   Powder/porous base materials to be used for hot water process        and oil-water separation can be made of a wide range of        materials including pure elemental metals, alloys, compounds,        combination of these with non-metallic materials, which can also        be used to form a nanostructured surface.    -   As another alternative, any type of powder/porous material        including insulators, conductors, semiconductors can be coated        with nanostructures of hot water process through a        cross-deposition mechanism. For example, a non-metallic porous        material can be places across a metal plate during HWT. The        molecules that migrate through water and deposit on metal        substrate to form nanostructures can also deposit on the        neighboring non-metallic porous material and can form a layer of        HWT-nanostructures.    -   Hot water process is applicable to almost any 3D material such        as powder, pipe, mesh, or foam that can be used for oil-water        separation applications.    -   A hot-water-process-nanostructured or pristine powder material        can be compressed by a variety of mechanical/sintering processes        (such as hot/cold press, metal printers, and direct metal laser        sintering) into different porous shapes and geometries (such as        disk, foam, etc. . . . ) which can be used in producing the        oil-water separator of this invention.    -   Nanostructure formation kinetics during hot water process can be        further enhanced by activating the surface with pretreatment        methods such as acid dipping (e.g. HF, HCL, and HNO₃) or plasma        exposure.    -   Fabricated powder/porous materials with special wettability        using the methods involved in this invention can be used to        remove all deferent types of liquids having surface energy        higher than that of water, including oils such mineral oils and        organic oils.    -   Fabricated powder/porous materials with special wettability        using the methods involved in this invention can be incorporated        into a wide variety of oil-water separation systems, including        filtration systems as filling materials in a cartridge unit or        tubular piping.    -   Fabricated powder/porous materials with special wettability        using the methods involved in this invention can be used in        other non-filtering methods of oil-water separation such as        powder to adsorb/absorb oils directly from the surface of        contaminated water.    -   Powder/porous materials used for oil-water separation can be        cleaned by a variety of physical and chemical methods and can be        used again for oil-water separation.

The foregoing description of the exemplary embodiments of the disclosurehas been presented only for the purposes of illustration and descriptionand is not intended to be exhaustive or to limit the disclosure to theprecise forms disclosed. Many modifications and variations are possiblein light of the above teaching.

The embodiments are chosen and described in order to explain theprinciples of the disclosure and their practical application so as toactivate others skilled in the art to utilize the disclosure and variousembodiments and with various modifications as are suited to theparticular use contemplated. Alternative embodiments will becomeapparent to those skilled in the art to which the present disclosurepertains without departing from its spirit and scope. Accordingly, thescope of the present disclosure is defined by the appended claims ratherthan the foregoing description and the exemplary embodiments describedtherein.

REFERENCE LIST

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What is claimed is:
 1. A method of synthesizing a composite usable foroil-water separation, comprising: surface nanostructuring pristinepowders to form nanostructured powders having surfaces with nanoscalefeatures; and coating single or multilayers of one or more low surfaceenergy oligomers, polymers, or their composites with other materials onthe surfaces of the nanostructured powders, wherein the surfacenanostructuring process comprises a hot water treatment (HWT) of thepristine powders, wherein the HWT is performed with the assistance ofmicrowave, infrared light heating, and/or in a high pressure container;and wherein the surface nanostructuring process comprises growing thenanoscale features on the surfaces of the pristine powders through across-deposition mechanism during the HWT.
 2. The method of claim 1,wherein the pristine powders comprise a metal, an alloy, a metal oxide,a compound of metals with non-metallic materials, a non-metallicmaterial, an insulator, a conductor, a semiconductor, or a combinationthereof.
 3. The method of claim 1, wherein the low surface energyoligomer or polymer has a surface energy lower than that of water andhigher than that of oil.
 4. The method of claim 3, wherein the compositeis hydrophobic or superhydrophobic, and oleophilic or superoleophilic,wherein the composite operably repels water and absorbs oil.
 5. Themethod of claim 1, wherein the low surface energy oligomer or polymerhas a surface energy lower than that of oil and higher than that ofwater.
 6. The method of claim 5, wherein the composite is oleophobic orsuperoleophobic, and hydrophilic or superhydrophilic, wherein thecomposite operably repels oil and absorbs water.
 7. The method of claim1, wherein the HWT comprises: mixing the pristine powders in water toform a mixture thereof; and heating the mixture at temperatures higherthan room temperature for a period of time to form the nanostructuredpowders having the surfaces with nanoscale features.
 8. The method ofclaim 1, wherein the cross-deposition mechanism comprises placing thepristine powders of non-metallic powders across a metal substrate duringHWT, wherein molecules that migrate through water and deposit on themetal substrate to form nanostructures deposit on the neighboringnon-metallic powders and form a layer of HWT-nanostructures.
 9. Themethod of claim 1, wherein the coating process is performed by a surfaceenergy reduction process including solution immersion and ovenevaporation.
 10. The method of claim 1, wherein the coating process isperformed by pulsed laser deposition, evaporative deposition, sputterdeposition, spray coating, paintbrush, or spin coating.
 11. The methodof claim 1, further comprising, prior to the surface nanostructuringprocess, a pretreatment process to activate the surface of the pristinepowders, wherein the pretreatment process includes acid dipping orplasma exposure.
 12. A method of synthesizing a composite usable foroil-water separation, comprising: surface nanostructuring a pristinepowder or porous material to form nanostructured powder or porousmaterial having surfaces with nanoscale features; and coating single ormultilayers of a self-assembled monolayer (SAM) polymer on the surfacesof the nanostructured powder or porous material, wherein the SAM polymeris 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (FDTS) or1-Dodecanethiol (DDT), wherein the surface nanostructuring processcomprises a hot water treatment (HWT) of the pristine powders, whereinthe HWT is performed with the assistance of microwave, infrared lightheating, and/or in a high pressure container, and wherein the surfacenanostructuring process comprises growing the nanoscale features on thesurfaces of the pristine powder or porous material through across-deposition mechanism during the HWT.
 13. The method of claim 12,wherein the pristine powder or porous material comprises a metal, analloy, a metal oxide, a compound of metals with non-metallic materials,a non-metallic material, an insulator, a conductor, a semiconductor, ora combination thereof.